Novel photographic elements

ABSTRACT

Color photographic elements having improved resistance to ultraviolet radiation, improved sharpness and low propensity to stain in the non-image areas comprise a paper support having coated thereon a silver halide emulsion layer which is sensitive to a visible region of the spectrum, which contains an incorporated color forming coupler. The paper support contains a non-fluorescing ultraviolet radiation absorbing compound and has, on its emulsion side surface, an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 m Mu .

United States Patent [191 Crawford et al.

[451 Sept. 3, 1974 NOVEL PHOTOGRAPHIC ELEMENTS [75] Inventors: Irvin H.Crawford; Francis M.

Hartman, both of Rochester, NY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: Sept. 26, 1972 [21] App]. No.: 292,365

Related US. Application Data [63] Continuation-in-part of Ser. No.447,373, April 12,

1965, abandoned.

[52] US. Cl. 96/74, 96/84 R, 96/84 UV, 96/85, 96/87 R [51] Int. Cl G03c1/84, G030 1/76 [58] Field of Search 117/333; 96/84 R, 84 UV, 96/85, 74

[56] References Cited UNITED STATES PATENTS 2,647,835 8/1953 Weaver96/84 R 2,698,235 12/1954 Swindells 96/87 OTHER PUBLICATIONS BritishTitan Products Co., Titanium Pigments, The Manfuacture And Uses,12-18-59, York, England,

PERCENT REF LE CTANCE N (u 0 Q WAVELENGTH IN MILLIMICRONS pages 11, 17,28 & 29.

British Titan Products Co., Technical Bulletin No. 2, York, England,12-1859, pages 2, 3 and 15.

Mellor, J. W., D. Sc., Comprehensive Treatise on Inorganic andTheoretical Chemistry, Longmans, Green & Co., N. N.Y., 1927, Vol. VII,pages 30-38.

Primary Examiner-Ronald H. Smith Assistant Examiner-Alfonso T. Suro PicoAttorney, Agent, or FirmMr. Henry E. Byers [5 7] ABSTRACT pound and has,on its emulsion side surface, an average reflectance of no more thanabout 25 percent over wavelengths'in the ultraviolet region of thespectrum in the range of about 360 to about 400 mp,

18 Claims, 2 Drawing Figures FOR CYAN IMAGE SENSITIVE EMULSION FORMAGENTA IMAGE SENSITIVE EMULSION COUPLER FOR YELLOW IMAGE BLUE-SENSITIVEEMULSION TITANIUM DIOXIDE POLYETHYLENE PAPER Pmmsnsrr 31914 PERCENTREFLECTANCE. U]

/COUPL ER FOR CYAN IMAGE RED-SENSITIVE EMULSION COUPLER FOR MAGENTAIMAGE GREEN- SENSITIVE EMULSION r I :COUPLER FOR YELLOW IMAGE,

BLUE-SENSITIVE EMULSION TITANIUM DIOXIDE K POLYETHYLENE PAPER WAVELENGTHIN MILLIMICRONS IRVIN H- CRAWFORD FRANCIS M HARTMAN INVENTORS ATTORNEYSNOVEL PHOTOGRAPHIC ELEMENTS This application is a continuation-in-partof U.S. Pat. Application Ser. No. 447,373 filed Apr. 12, 1965 nowabandoned.

This invention relates to novel photographic elements. Moreparticularly, this invention relates to color photographic papers whichyield dye images resistant to ultraviolet radiation.

Color photographs, particularly where the dye images are formed insensitive silver halide emulsion layers by color development, aresusceptible to fading and discoloration by the action of ultravioletradiation to which the photographs are subjected during viewing.Furthermore, residual couplers contained in the emulsion layers afterformation of the picture images in certain processes are attacked byultraviolet radiation and form a yellow stain (background stain) whichis undesirable in the finished photograph.

The action of ultraviolet radiation on finished color photographs isparticularly noticeable in positive prints on paper supports, since thistype of print is frequently viewed in daylight. It is also desirable forcolor prints on paper supports to have sharp images and in many cases tohave glossy surfaces. These glossy surfaces are usually achieved bydrying the processed print in faceto-face contact with the surface of ahot drum which requires the emulsion surface to be highly hardened toprevent sticking or melting of the emulsion which would result insurface mottle. It is difficult, however, to highly harden photographicelements containing dye-forming couplers since hardeners tend to reactwith the couplers. It is evident, therefore, that a photographic elementin which the aforementioned undesirable characteristics are improved oreliminated would enhance the state of the art.

Accordingly, it is an object of this invention to provide a novelphotographic element.

Another object of this invention is to provide color photographic paperswhich can be processed to produce dye images having a high resistance toultraviolet radiation.

Another object of this invention is to provide a method for preparingcolor photographic papers which can be processed to produce dye imageshaving a high resistance to ultraviolet radiation.

Another object of this invention is to provide color photographic paperswhich can be processed to produce color photographs which have a lowpropensity to stain in the non-image areas.

Still another object of this invention is to provide color photographicpapers which can be processed to produce dye images having highresistance to ultraviolet radiation, improved sharpness and which can beprocessed to produce glossy prints without drying in face-to-facecontact with a smooth surface.

In accordance with this invention it has'been found that a paper supportcontaining a non-fluorescing ultraviolet radiation absorbing compoundand having reflectance characteristics on its emulsion side surface asdescribed herein, significantly improves resistance to fading and yellowstain and, in certain cases, sharpness of multicolor photographic layerscoated over the support. Furthermore, the use of an additionalultraviolet absorbing layer or layers over one or more of thecolorforming photographic layers results in a still further improvementin quality.

It is well known that ultraviolet radiation absorbing layers can beplaced over dye images to screen out ultraviolet radiation to reduce dyefading. 'However, it could not have been predicted that a support, asdescribed herein; could improve the resistance to fading of multicolorlayers coated thereon since the ultraviolet absorber in the support isunder, rather than over, the photographic color layer or layers.Furthermore, it would have been expected that such a support would addno significant improvement to the dye stability of an incorporatedcoupler containing emulsion layer lying between it and an ultravioletfilter layer. However, as shown in Example 5 which follows, there is asignificant improvement achieved by using an ultraviolet filter layer incombination with the support having the reflectance characteristicsdescribed herein.

The incorporation of the ultraviolet radiation absorbing compounds intothe support, as in this invention, rather than into a photographicemulsion layer or layers between photographic emulsions, offers severalsignificant advantages. For example, the incorporation of an ultravioletabsorbing compound into a photographic emulsion layer can lead tocontamination and desensitization. Furthermore, when oilsolubleultraviolet radiation absorbers are incorporated into a photographicemulsion layer or an interlayer, they tend to create opalescence in awet processed print which makes it difficult to judge color qualityuntil the print is dry. If water soluble ultraviolet radiation absorbersare employed the viscosity of the melts are increased to a point wheresevere coating problems are encountered. Incorporating the ultravioletradiation absorber into the support where it is firmly held overcomessuch problems.

A significant feature of this invention is that when titanium dioxide isemployed asthe non-fluorescing ultraviolet absorbing compound, onlycertain physical forms are satisfactory, as shown in Example 3 whichfollows. Furthermore, fillers such as barium sulfate, which are oftenemployed to whiten photographic paper, do not impart therequiredReflectance to the paper support. Therefore, such materials, inthe absence of a suitable ultraviolet radiation absorber, cannot beemployed in practicing this invention, as shown in Example 1, whichfollows.

The paper support employed in the practice of this invention mustexhibit an average Reflectance, on its emulsion side surface, of no morethan about 25 percent over wavelengths in the ultraviolet region of thespectrum in the range of about 360 to about 400 rnu,

preferably about 380 to about 400 mu. In combination with theaforementioned average reflectance, the paper support generally has aprofile in which the Reflectance, on its emulsion side surface, is nomore than about 10 percent, preferably not more than about 8 Reflectanceis that fraction of light which is reflected from the surface of theopaque paper support at the defined wavelength of the spectrum, and canbe determined using any method suitable for this purpose. For example, astandard recording spectrophotometer can be employed to measureReflectance at different wavelengths over the range of about 360 toabout 400 mp. Typically a Hardy General Electric RecordingSpectrophotometer (Stovepipe Model) is employed in which an integratingsphere is used to measure diffuse reflectance according to the C.I.E.recommended standards geometry 8/D. Typical reflectance curves are shownin VanCampen US. Pat. No. 2,956,879 issued Oct. 18, 1960.

When averaged, the reflectance at the wavelengths over this range mustbe less than 25 percent if the support is to be used in the practice ofthis invention. This average Reflectance is exhibited by the surface orsurfaces of the paper support over which photographic emulsion layerscontaining an incorporated coupler are coated. Such surfaces arereferredto herein as the emulsion side surface of the paper support. Theultraviolet absorbing compounds in the support absorb radiation in theultraviolet region of the spectrum and do not emit absorbed radiation inthe visible region of the spectrum, i.e., they are non-fluorescent. Anyultraviolet radiation absorbing compound which will impart the requiredreflectance to the support can be used in the practice of thisinvention. The ultraviolet radiation absorbing compound can beinorganic, as exemplified by metal oxides such as zinc oxide andtitanium dioxide, preferably titanium dioxide of the rutile crystalstructure. Various average particle size ranges may be used provided thedesired reflectance values are obtained. For instance, rutile titaniumdioxide used to provide desired reflectance values measured with anoptical microscope preferably has an average particle size of about 0.5to about microns. However, the average particle size can be variedwidely and values for average particle size measured on an electronmicroscope typically appear to have an average particle size of 0. 19 to0.4 micron indicating that possibly agglomerates of smaller particlesare measured on an optical microscope.

Good results are also obtained in practicing this invention with organicnon-fluorescing ultraviolet absorbing bensotriazoles of the typedisclosed in Belgian Pat. No. 623,419 and German Pat. No.. 1,166,623.These pounds. have th rmula:

wherein R, R and R can each represent a hydrogen atom, a halogen atom,such as chlorine, bromine, iodine, etc., a nitro group, an alkyl grouphaving from 1 to 18 carbon atoms such as methyl, ethyl, propyl,isopropyl, aminopropyl, butyl, sec-butyl, chlorobutyl, amyl, isoamyl,hexyl, octyl, nonyl, stearamidobutyl, decyl, dodecyl, pentadecyl,hexadecyl, octadecyl, cyclohexyl, benzyl, phenylethyl, phenylpropyl,etc., an alkoxy group having from one to 18 carbon atoms, such asmethoxy, propoxy, chlorobutoxy, decoxy, nonoxy, diamylphenoxyethoxy,pentadecoxy, octadecoxy, carhomcthoxy, carbobutoxy, carbohexoxy,carbododecoxy, carbopentadecoxy, etc., an aryl group, such as phenyl,4-methylphenyl, 4-ethoxyphenyl, 2- hexoxyphenyl, 3-hexoxyphenyl, etc.,an aryloxy group, such as phenoxy, 4-methylphenoxy, 2-propylphenoxy,3-amylphenoxy, etc., such that at least one of the groups, R, R and Rshall contain at least five carbon atoms, and the total numberof carbonatoms represented in R R is at least 8. Suitable compounds of this typeinclude, for example, 2 -(2 -hydroxy-5-noctylphenyl)benzotriazole, 2-(2-hyd roxy-3 ,5 -di tert-amylphenyl)benzotriazole, 2-(2-hydroxy-3-tert-2-(2 -hydr0xy-3 -n-butyl-5"-tert-amyl phenfflbenzotriazole, chl0ro-2(2-hydr0xy-3 -tert-butyl-5 -cyclohexylphenyl)benzotriazole, 5-methyl-2 (2'-hydroxy- 3 -tert-amyl-5 '-phenoxyphenyl)benzotri azole, and the like.

Another class of organic ultraviolet radiation absorbing thiazolidoneswhich can be used with advantage in this invention are disclosed in US.Pat. No. 2,739,888 which issued Mar. 27, 1956. These compounds have theformula:

wherein R represents a hydrogen atom, an alkyl group (e.g., methyl,ethyl, ,B-hydroxyethyl, B-sulfoethyl, B-diethoxyethyl, propyl,isopropyl, butyl, isobutyl, amyl, hexyl, heptyl, octyl, nonyl, decyl,lauryl, cetyl, etc.), a cycloalkyl group (e.g., cyqlopentyl, cyclohexyl,etc. an aryl group (e.g.,phenyl, o-, mand p-tolyl, o-, mandp-ethylphenyl, p-i'sopropylphenyl, pamylphenyl, o-, mandp-methoxyphenyl, o-, mand p-ethoxyphenyl, ,B-hydroxyethylphenyl, o-,mand pchlorophenyl, o-, mand p-hydroxyphenyl, o-, mand p-sulfophenyl(and alkali metal salts thereof, e.g., sodium, potassium etc.),4-methoxy-3-sulfophenyl (and alkali metal salts thereof, e.g., sodium,potassium, etc. 2,4-dicarboxymethylphenyl (and alkali metal saltsthereof, e.g., sodium, 'potassium, etc.), o-, mand pcarboxyphenyl (andalkali metal salts thereof, e.g., sodium, potassium, etc.),3-(3sulfobenzamido)phenyl (and alkali metal salts thereof, e.g., sodium,potassium, etc.), o-carbobutoxyphenyl, diamylphenoxyacetoxyphenyl, etc.,or an aralkyl group (e.g., benzyl, ,B-phenylethyl, a-phenylethyl, etc.),R represents an aryl group (e.g., those aryl groups defined abovewherein R is an aryl group), and Q represents a divalent, non-metallicatom (e.g., oxygen, sulfur, etc.) or imino radical (e.g., imino,phenylimino, o-, m-. and pchlorophenylimino, benzylimino,B-phenylethylimino, a-phenylethylimino, o-, mand p-tolylimino, o-, mandp-ethylphenylimino, p-amylphenylimino, o-, mand pethoxyphenylimino, etc.Typical compounds of this type include, for example,5-benzylidene-3-ethyl-2- phenylimino-4-thiazolidone, 5-p-methylbenzal-3-phenyl-Z-phenylimino-4-thiazolidone,5-mnitrobenzal-3-phenyl-2-phenylimino-4-thiazolidone,5-benzal-3-methyl-2,4-thiazolidinedione, 5 -benzal-3-n-cetyl-2phenylimino-4-thiazolidone and 3-p-(B-hydroxyethyl)phenyl-2-p-(,B-hydroxyethyl)phenyl-S-(4-methoxy-3-sulfobenzal)-4-thiazolidone.

The ultraviolet radiation absorbing compounds can be incorporated intothe paper support using any procedure which is suitable for thispurpose. For example, the paper forming the support can be impregnatedwith the ultraviolet absorbing compound during its manufacture. However,it is generally more desirable to dissolve or disperse the ultravioletabsorbing compound in a solvent medium together with a colloidal bindersuch as gelatin, a cellulose ester such as cellulose acetate, asynthetic resin such as polyvinyl acetal, hydrolyzed polyvinyl acetate,polyolefins, or the like, and coat the resulting mixture on the emulsionside of the paper. This results in a paper support containing a vehicle,e.g., polyethylene impregnated with the ultraviolet absorber.Particularly advantageous results are obtained with inorganicultraviolet absorbing radiation com-' pounds such as titanium dioxidewhere polyolefins such as polyethylene, polypropylene, propylene-butenecopolymers, and the like, are used as binding agents for the ultravioletradiation absorber. In this case, the ultraviolet absorbing compoundssuch as titanium dioxide are dispersed in polyolefin, preferablypolyethylene, in a concentration of about 3 to about percent, preferablyabout 6 to about 13 percent, by weight. The dispersion can then becoated at a concentration of about 1 to about 11, preferably about 3 toabout 8 grams/ft of paper substrate. It should be understood that theterm support, when employed herein, includes a support of paper stockimpregnated with the ultraviolet absorbing compound as well as paper inwhich the ultraviolet radiation absorber is impregnated in a coating,e.g., a polyolefin coating forming a part of the support. It otherwords, the support is the foundation upon which at least one lightsensitive photographic layer containing a dye-forming or color coupleris superimposed.

In addition to the ultraviolet radiation absorbing compound contained inthe support, a photographic element of this invention can also beprovided with an ultraviolet filter layer over at least one color layerwhich is subject to the harmful effects of ultraviolet radiation. Forexample, in a multilayer material comprising three differentiallysensitized layers, the red sensitive layer being adjacent to thesupport, the green sensitive layer being superimposed on the redsensitive layer and the blue sensitive layer being outermost withrespect to the other light sensitive layers; the ultraviolet filterlayer can be placed between the blue and green sensitive layers. Theconcentration of ultraviolet absorbing compound employed in the papersupport according to this invention can be varied depending upon theeffect desired and the use to which the photographic element is to beput. However, it is generally desirable to employ a concentration ofultraviolet absorbing compound that is at least 50 milligrams, andgenerally up to about 3 grams per square foot of support to obtain therequired average reflectance.

The coupler containing emulsions employed in the practice of thisinvention will ordinarily comprise the emulsion layers of multilayercolor films which emulsion layers are customarily differentiallysensitized to the primary regions of the visible spectrum and containcoupler compounds producing dye images colored complementary to thesensitivity of the emulsion layers. In a typical color film, emulsionssensitized to the red, green and blue regions of the spectrum aresuperimposed on the support described herein and contain cyan, magentaand yellow color-forming coupler compounds, respectivelyiA yellow filterlayer such as Suitable silver halides include, for example, silverchloride, silver chlorobromide, silver chloroiodide, silverchlorobromoiodide, silver bromoiodide and the like. Emulsions which forma latent image mostly inside the silver halide grains can be employed inthe practice of this invention. Furthermore, packet emulsions, i.e.,emulsions in which a silver halide and a color forming coupler areincorporated in a discrete packet within an emulsion layer with otherdiscrete packets of silver halide containing other color formingcouplers, can be employed. The dispersing agent for the photographicsilver halide can be gelatin or other hydrophilic material such ascolloidal albumin, cellulose derivatives, synthetic resins, such aspolyvinyl compounds, acrylamide polymers and the like.

The photographic silver halide emulsions employedin this invention arespectrally sensitized or unsensitized. The usual spectral sensitizingdyes used include, for example, the cyanines, merocyanines, complex-(trinuclear)cyanines, complex(trinuclear)merocyanines, styryls,hemicyanines and the like. These dyes can contain the conventional basicnuclei such as triazole, benzotriazole, naphthotriazole, benzoxazole,naphthoxazole, benzoselenazole, benzimidazole, quinoline, etc., or inthe case of merocyanine dyes such nuclei as rhodanine, 2-thiohydantoin,oxazoledione, pyrazolone, etc. Such dyes, for example, are described inBrooker U.S. Pat. No. 2,185,182 issued Jan. 2, 1940, Brooker U.S. Pat.No. 2,241,237 issued May 6, 1941, Carroll U.S. Pat. No. 2,635,961 issuedApr. 21, 1953, Carroll U.S. Pat. No. 2,652,330 issued Sept. 15, 1953,Heseltine and Brooker U.S. Pat. No. 2,666,761 issued Jan. 19, l954-andCarroll and Jones U.S. Pat. No. 2,704,715 issued Mar. 22, 1955.

The coupler compounds used in the emulsion layers which are coated overthe paper support described herein can be any of the well knowncompounds which combine with the oxidation products of primary aromaticamino silver halide color developing agents to form dyes. Suitablecoupler compounds include, for example, the phenolic compounds vof U.S.Pat. Nos. 2,266,452, 2,363,598, 2,589,004, 2,474,293, 2,521,908, and2,423,730; the pyrazolone compounds of U.S. Pat. Nos. 1,969,479,2,369,489, 2,600,788, 2,618,641, and 2,51 1,231 and the open chainreactive methylene compounds of U.S. Pat. Nos. 2,298,443, 2,652,329,2,407,210 and 2,271,238. Likewise, the emulsions can contain colorcoupler forming compounds as described in U.S. Pat. Nos. 2,706,684,2,455,169, 2,694,703, 2,455,170 and 2,453,661. The couplers can bedispersed in the emulsion layers by means of an oily coupler solventaccording to the methods of U.S. Pat. Nos. 2,304,940 and 2,322,027.However, if as may be the case, the couplers contain solubilizing groupssuch as 1-1 groups which render the compounds soluble in alkalisolution, the oily coupler solvent can be dispensed with and the couplercan be added to the emulsion from aqueous solution as the alkali metalsalt.

This invention can be further illustrated by reference to theaccompanying drawings in which:

FIG. 1 is a diagrammatical cross-sectional view of a multicolor elementaccording to the invention;

FIG. 2 is a set of reflectance curves for four supports containing twodifferent physical forms of titanium dioxide, barium sulfate or zincoxide.

in FIG. 1 there is shown a cross-sectional view of a photographic colorelement of the type which can be advantageously employed in the practiceof this invention. The element comprises a support 1 of paper stockcontaining titanium dioxide dispersed in polyethylene. The elementcontains a blue sensitive silver halide emulsion layer 2, coated on topof the support. The blue sensitive emulsion can contain a coupler orcolor forming compound which reacts with the oxidation product of thecolor developer to produce a yellow image. Coated on top of the bluesensitive layer is a green sensitive silver halide emulsion layer 3which can contain a coupler or color forming compound capable ofcoupling with the oxidation product of the color developer to produce amagenta'image. The element shown has an outermost red sensitive silverhalide emulsion layer 4 which is coated on top of the green sensitivelayer. The red sensitive layer can contain a coupler or color formingcompound capable of coupling with the oxidation product of the colordeveloper to produce a cyan image. The support illustrated, if desired,can also contain additional layers (not shown) such as gelatin layers,subbing layers, antihalation layers, and the like.

FIG. 2 gives the reflectance curves for four paper supports containing(A) titanium dioxide predominately of the rutile crystal structure, asshown in Examples l and 3, (B) barium sulfate, as shown in Example 1,(C) zinc oxide, as shown in Example 7 and (D) titanium dioxide,predominately of the anatase crystal structure, as shown in Example 3.

In Curve A, the percent reflectance value of about 7 at the 360 line andabout 38 at the 400 line can be added together and divided by 2 to givea value of about 23 percent.

Curve B is interpreted in a similar way by adding 50 and 73 together anddividing by 2 to give a value of 6 percent.

Since Curve C is not a straight line due to the curve in the toe portionof the curve, segments of the curve are treated as separate straightline portions and the values read at increments of about 10millimicrons. Therefore, the value at 360 is about 5; 370 about 5; 380about 390 about 35; and 400 about 65. The sum of these values is about115 which, when divided by 5, gives an average percent reflectance of 23percent which is less than the specified 25 percent.

Curve D which approximates a straight line over the section between 360and 400 millimicrons provides an average reflectance value by addingabout 1 1 and about 63 which, when divided by 2, equals about 37 percentas given in Example 3 for average reflectance of the support at 360-400millimicrons.

The coupler containing silver halide emulsions employed in thisinvention can also contain such addenda as chemical sensitizers, e.g.,sulfur sensitizers (e.g., allyl thiocarbamide, thiourea,allylisothiocyanate, cystine, etc.), various gold compounds (e.g.,potassium chloroaurate, auric trichloride, etc.) (see Baldsiefen U.S.Pat. No. 2,540,085 dated Feb. 6, 1951, Damshroder U.S. Pat. No.2,597,856 dated May 27, 1952 and Yutzy and Leermakers U.S. Pat. No.2,597,915 dated May 27,

1952), various palladium compounds such as palladium chloride(Baldsiefen et al U.S. Pat. No. 2,540,086 dated Feb. 6, 1951), potassiumchloropalladate (Stauffer and Smith US. Pat. No. 2,598,079 dated May 527, 1952) etc., or mixtures of such sensitizers, antifoggants, such asammonium chloroplatinate (Trivelli and Smith U.S. Pat. No. 2,566,245dated Aug. 28, 1951), ammonium chloroplatinite (Trivelli and Smith U.S.Pat. No. 2,566,263 dated Aug. 28, 1951), benzotriazole,nitrobenzimidazole, S-nitroindazole, benzidine, mercaptans, etc. (seeMees The Theory of the Photographic Process, MacMillian Pub. 1942, page460) or mixtures thereof, hardeners such as aldehyde hardeners,aziridine-hardeners, hardeners which are derivatives of dioxane,oxypolysaccharides such as oxystarch or oxy plant gums and other typesof hardeners for gelatin and hydrophilic colloids. Dispersing agents forcolor couplers, such as those set forth in Jelley and Vittum U.S. Pat.No. 2,322,027 dated June 15, 1943 and Marines and Godowsky U.S. Pat. No.2,304,940 dated Dec. 15, 1942 can also beemployed in the above describedemulsions. v

The following examples are included for a further understanding of theinvention.

Example 1 As already indicated, a paper support containing anon-fluorescent ultraviolet absorbing compound and having the requiredreflectance provides a multicolor photographic element exhibitingimproved resistance to image dye fading. Furthermore, compounds such asbarium sulfate which have been used as fillers to whiten photographicpaper do not impart the required reflectance to the support. Toillustrate, a paper support is prepared by coating a paper fiber sheetwith a baryta layer (barium sulfate, average particle size about 2microns in diameter, dispersed in gelatin and coated at a coverage ofabout 3 g. of barium sulfate/ft? The baryta surface of the support hasan average Reflectance of 40 about 63 percent between 360 and 400 mm. Asecond support is prepared by coating the above baryta coated paperfiber sheet with titanium dioxide of rutile crystal structure dispersedin gelatin at a coverage of about 300 mg of titanium dioxide and 300 mgof gelatin/ft? The surface of the support has an average reflectance ofabout 17 percent between 360 and 400 mu.

Eachof the above supports is coated with a series of photographic layersto produce a multicolor photographic element comprising thesupporthaving coated thereon in the following order:

1. a blue sensitive gelatino silver chlorobromide emulsion containing anopen chain coupler for the yellow image, such as' one of the yellowcouplers described in McCrossen et a] U.S. Pat. No. 2,875,057, e.g.,4-benzoylacetamido-3-methoxy- (2,4'-di-tert-amylphenoxy )-acetanilide;

2. a gelatin interlayer;

3. a green sensitive gelatino silver chlorobromide emulsion containing apyrazolone coupler for the magenta image, such as one of the pyrazolonecouplers described in Loria et al U.S. Pat. No. 2,600,788, e.g.,l-(2,5-dichlorophenyl)3[3"-(2,4"'-di-tert-amyl-phenoxyacetamido)benzamido]-5-pyrazolone;

4. a gelatin interlayer;

5. a red sensitive gelatino silver chlorobromide emulsion containing aphenolic coupler for the cyan image, such as one of the phenoliccouplers described four days to a Xenon arc, the following results areobin Fierke US. Pat. No 2,801,171, e.g., rai d;

Average rcllccluncc Back- Paper Support of the Support Magenta Ycllowground Containing at 360-400 mp. Dye Loss Dye Loss Stain Baryta 63% 36%17% Aryl imino thia- 6% 26% 12% 2% zolidone Aryl benzotriazole 6% 28% 11% 2% 6-{ {a-{4-[a-(2 ,4-di-tert-amylph enoxy)-butyr- Example .3

amido]phenoxy}-acetamido}}2,4-dichloro-3- methylphenol;

6. a gelatin protective overcoat.

The multicolor photographic elements are exposed and processed asdescribed in Example 1 of US. Pat.-

No. 2,956,879 to produce color dye images. When the processed stripscontaining the dye images are exposed to ultraviolet radiation, e.g.,four days to a Xenon arc, the following results are obtained:

Paper Support Magenta Yellow Background Containing Dye Loss Dye LossStain Baryta 36.7% 17% 5% Titanium dioxide 28.6% 13% 1% The Magenta DyeLoss and Yellow Dye Loss, as reported herein, are measured in the greenand blue regions of the spectrum, respectively, using a conventionalspectrophotometer or a densitometer through an Example 2 The inorganicnon-fluorescent ultraviolet radiation absorbing compounds such as themetal oxides, particularly titanium dioxide, are preferred in thepractice of this invention. However, the organic non-fluorescentultraviolet radiation absorbing compounds can be employed. Thus, aseries of paper supports, prepared as described in Example 1 except thatorganic ultraviolet absorbers are incorporated in the support over thebaryta surface, are coated with a series of layers to produce amultilayer photographic element as described in Example 1. One supporthas an aryl imino thiazolidone of the type described in Sawdey U.S. Pat.No. 2,739,888, dispersed in gelatin, incorporated in the surface of thesupport and the other support has an aryl benzotriazole of the typedescribed in German Pat. No. 1,166,623 and Belgian Pat. No. 623,419dispersed in gelatin, incorporated in the surface at a coverage of about150 mg of the ultraviolet absorber and 300 mg of gelatin/ft? Thesesupports have the Reflectance characteristics indicated in the followingtable. The multicolor photographic elements are exposed and processed asdescribed in Example 1 of US. Pat. No. 2,956,879 to produce colorimages. When the processed strips containing the dye images are exposedfor As previously pointed out, not all physical forms of titaniumdioxide can be employed in the practice of this invention to giveoptimum results. To illustrate, two paper supports prepared as describedin Example 1 with titanium dioxide having different crystal structures.Titanium dioxide containing about 100 percent by weight rutile on onesupport and containing about 85 percent by weight anatase in the coatingon the other support are coated with a series of layers to produce amultilayer photo graphic element. When these elements are exposed,processed and tested as described in Example 1, the followingcharacteristics are observed:

Average reflectance Crystal structure of the support (Predominately) at360-400 my Background stain Rutile 16% 1% Anatase 37% 5% Example 4 niumdioxide/ft? The paper supports having the polyethylene surfaces areelectron bombarded as described in British Pat. No. 971,058. Each ofthese supports is coated with a-series of emulsion layers to provide amulticolor photographic element as described in Example 1. Themulticolor photographic elements are exposed and processed as describedin Example 1 to produce color dye images. When the processed stripscontaining the dye images are exposed four days to a Xenon arc thefollowing results are obtained:

Average reflectance Paper support Magenta Background of the supportcontaining dye loss stain at 360-400 mp.

Polyethylene 26% Increases 58% Polyethylene- 21% Decreases 16% titaniumdioxide in Example 3, has the sharpest images. A further increase insharpness is obtained by including absorbing dyes in the emulsion layersof the photographic element. These dyes absorb in the same region of thespectrum to which the emulsion is sensitive. Suitable absorbing dyes aredescribed in U.S. Pat. Nos. 2,956,879, 2,629,658 and 2,947,628. Ifdesired, a polyethylene layer can be coated on each surface of the paperfiber sheet.

In addition, the multilayer element coated on the paper supports withthe polyethylene surfaces give glossy prints when dried on a hot drumwith the back of the paper in contact with the drum surface or whendried by air impingement upon the emulsion side of the element. Theprocessed element on the baryta support of Example 1 does not produceglossy prints when dried in this manner.

Similar improvements are obtained when paper supports having an averagereflectance of less than about 25 percent between 360 and 400 mu arecoated with single layer mixed packet multicolor elements of the typedescribed in U.S. Pat. Nos. 2,168,182, 2,698,765, 2,698,766 and2,965,484.

Example 5 The combination of an ultraviolet filter layer with theparticular type of paper support described herein gives a completelyunexpected improvement in fading characteristics. To illustrate, twomultilayer color coatings are made of the polyethylene-titanium dioxidesurface support described in Example 4. The support is coatedUltraviolet absorbing Magenta dye loss interlayer Absent 25% Present 22%Example 6 The concentration of the ultraviolet absorber in the surfaceof the support is subject to wide variation. However, there must besufficient ultraviolet absorber present to provide a support having anaverage reflectance of less than about 25 percent between 360 and 400m,u. To illustrate, multilayer color coatings are made as described inExample 1 on a series of paper supports having different concentrationsof titanium dioxide on the surface. In each case the supports have anaverage reflectance less than 25 percent between 360 and 400 mu. Whenthese multicolor elements are exposed, processed and tested as describedin Example 1, the following results are obtained:

A further improvement in image dye fading and resistance to backgroundstain is obtained by incorporating in one or more of the emulsion layersa hydroxysubstituted aromatic antistain agent such as an antistain agentdescribed in Loria et al U.S. Pat. No. 2,728,659, Thirtle et al U.S.Pat. 'No. 2,701,197, 2,360,290, 2,991,177 and 2,735,765, e.g., alkylsubstituted hydroquinones and alkyl substituted phenols.

Example 7 Titanium dioxide is preferably employed in the practice ofthis invention. However, other inorganic nonfluorescent compounds can beemployed. Thus, a paper support having a zinc oxide-polyethylene surfaceis prepared by coating zinc oxide dispersed in polyethylene on a paperfiber sheet at a coverage of about 0.80 g of polyethylene and 0.33 g ofzinc oxide/ft". A second support having a titanium dioxide-polyethylenesurface is prepared by coating titanium dioxide dispersed inpolyethylene on a paper fiber sheet at a coverage of about 0.70 g ofpolyethylene and 0.125 g of titanium dioxide/ft Multilayer colorcoatings are made, using these supports, as described in Example 1.These elements are exposed and processed through a reversal colorprocess of the type described in Example 2 of U.S. Pat. No. 2,944,900.When the processed strips containing the dye images are exposed for 10days to daylight in a north window, the following results are obtained:

Average reflectance The photographic coating on the titanium dioxidesurface exhibits sharper images than the coating on the zinc oxidesurface.

Thus, by the practice of this invention there is provided a uniquephotographic element comprising multilayer incorporated coupleremulsions superimposed upon a paper support which element exhibitsimproved resistance of fading and yellow stain as well as increase inthe sharpness of the photographic image. The support employed inpracticing this invention can contain the non-fluorescent ultravioletabsorbing compounds described herein as the sole ultraviolet absorber orit can contain additional ultraviolet absorbers, fluorescent ornon-fluorescent, so long as the additional addenda do not deleteriouslyaffect the Reflectance characteristics of the support. Suitableadditives of this type include, for example, filler type substances suchas barium sulfate, silicon dioxide, or other whiteners generallyemployed in photographic paper supports.

Although the invention has been described in considerable detail withreference to certain preferred embodiments thereof, it will beunderstood that variations and modifications can be effected withoutdeparting from the spirit and scope of the invention as describedhereinabove and as defined in the appended claims.

We claim:

1. A photographic element comprising a silver halide emulsion layerwhich is sensitive to a visible region of the spectrum and contains anincorporated color forming coupler, said layer being coated upon asurface on a paper support, said surface comprising a polyolefinimpregnated with an ultraviolet radiation absorbing compound which doesnot emit any substantial amount of absorbed radiation in the visibleregion of the spectrum, said polyolefin surface having an averagereflectance of no more than about 25 percent over wavelengths in theultraviolet region of the spectrum in the range of about 360 to about400 millimicrons and at least about 60 percent, at a wavelength in thevisible region of the spectrum in the range of about 420 to about 500mu.

2. A photographic element comprising a silver halide emulsion layerwhich is sensitive to a visible region of the spectrum and contains anincorporated color forming coupler, said layer being coated upon asurface on a paper support, said surface comprising polyethyleneimpregnated with an ultraviolet radiation absorbing compound which doesnot emit any substantial amount of absorbed radiation in the visibleregion of the spectrum, said polyethylene surface having an averagereflectance of no more than about 25 percent over wavelengths in theultraviolet region of the spectrum in the range of about 360 to about400 millimicrons and at least about 60 percent, at a wavelength in thevisible region of the spectrum in the range of about 420 to about 500mu.

3. A photographic element of claim 1 in which said silver halideemulsion has coated thereon an ultraviolet radiation absorbing compound.

4. A photographic element of claim 1 in which said silver halideemulsion layer contains a hydroxysubstituted aromatic antistain agent.

5. A photographic element comprising a silver halide emulsion layerwhich is sensitive to a visible region of the spectrum and contains anincorporated color forming coupler, said layer being coated upon asurface on a paper support, said surface comprising polyethyleneimpregnated with titanium dioxide, said polyethylene surface having anaverage reflectance of no more than about 25 percent over wavelengths inthe ultraviolet region of the spectrum in the range of about 360 toabout 400 millimicrons and at least about 60 percent, at a wavelength inthe visible region of the spectrum in the range of about 420 to about500 mu.

6. A photographic element of claim in which said titanium dioxide ispredominately rutile titanium dioxide.

7. A photographic element of claim 5 in which said titanium dioxide isemployed in a concentration of from 50 milligrams to about 3 grams persquare foot.

8. A photographic element of claim 1 in which the ultraviolet radiationabsorbing compound is a benzotriazole.

9. A photographic element of claim 1 in which the ultraviolet radiationabsorbing compound is a thiazolidone.

10. A photographic element of claim 1 in which said coupler is anincorporated pyrazolone magenta coupler and said visible region of thespectrum is the green region.

11. A photographic element comprising:

a. a silver halide emulsion layer having a blue sensitive layercontaining an incorporated yellow forming coupler,

b. a silver halide emulsion layer containing a red sensitive layercontaining an incorporated cyan forming coupler, and

c. a green sensitive layer containing a magenta forming coupler,

d. said layers being coated upon a surface on a paper support,

e. said surface comprising a polyolefin impregnated with titaniumdioxide,

f. said polyolefin surface having an average reflectance of no more thanabout 25 percent over wavelengths in the ultraviolet region of thespectrum in the range of about 360 to about 400 millimicrons and atleast about percent, at a wavelength in the visible region of thespectrum in the range of about 420 to about 500 mu.

12. A photographic element of claim 11 in which said titanium dioxide ispredominately rutile titanium dioxide.

13. A photographic element of claim 11 in which said polyolefin ispolyethylene.

14. A photographic element comprising a developed and fixed photographicemulsion layer containing a developed dye image subject to fading by theaction of ultraviolet radiation, said layer being coated upon a surfaceon a paper support, said surface comprising a polyolefin impregnatedwith an ultraviolet radiation absorbing compound, which does not emitany substantial amount of absorbed radiation in the visible region ofthe spectrum, said polyolefin surface having an average reflectance ofno more than about 25 percent over wavelengths in the ultraviolet regionof the spectrum in the range of about 360 to about 400 millimicrons andat least about 60 percent, at a wavelength in the visible region of thespectrum in the range of about 420 to about 500 mu.

15. A photographic element comprising a developed and fixed photographicemulsion layer containing a developed dye image subject to fading by theaction of ultraviolet radiation, said layer being coated upon a surfaceon a paper support, said surface comprising a polyolefin impregnatedwith titanium dioxide, said polyolefin surface having an averagereflectance of no more than about 25 percent over wavelengths in theultraviolet region of the spectrum in the range of about 360 to about400 millimicrons and at least about 60 percent, at a wavelength in thevisible region of the spectrum in the range of about 420 to about 5001..

16. A photographic element comprising a developed and fixed photographicemulsion layer containing a developed dye image subject to fading by theaction of ultraviolet radiation, said layer being coated upon a surfaceon a paper support, said surface comprising polyethylene impregnatedwith titanium dioxide, said polyethylene surface having an averagereflectance of no more than about 25 percent over wavelengths in theultraviolet region of the spectrum in the range of about 360 to about400 millimicrons and at least about 60 percent, at a wavelength in thevisible region of the spectrum in the range of about 420 to about 500 u.

17. A photographic element of claim 16 in which said titanium dioxide ispredominately rutile titantium dioxide.

18. A photographic element comprising a developed and fixed photographicemulsion layer containing a developed dye image subject to fading by theaction of ultraviolet radiation, said layer being coated upon a surfaceon a paper support, said surface comprising polyethylene impregnatedwith 50 milligrams to about 3 grams per square foot of titanium dioxidepredominately rutile form, said polyethylene surface having an averagereflectance of no more than about 25 percent the visible region of thespectrum in the range of about over wavelengths in the ultravioletregion of the spec- 420 to about 500 11..

trum in the range of about 360 to about 400 millimicrons and at leastabout 60 percent, at a wavelength in UNITED STATES PATENT AND TRADEMARKOFFTICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,833,380 i b DATEDSeptember 3, 197

INVENTOR( Irvin H. Crawford and Francis M. Hartman It is certified thaterror appears in the aboveiden tified patent and that said LettersPatent are hereby corrected as shown below:

Column l, line 1 r, "triazole, chloro- 2(2'hydroxy-3'-tert-butyl-5'-cyclo-" should read triazole, 5-chloroi2-(2'hydroxy-3'-tertbutyl5' -cyclo I Column 6, line 2, "low" should read--yellow--.

Column 12, line A l, "of fading should read ---to fading-5 line LL14,after "as well as" insert -an--.

Column 1h, line M5, "500 1" should read ---5oo milp line 57, "500 1"should read ---5OO mp1---.

Column 16, line 2, "500 )1" should read --5OO rrr,u. g

Signed and Scaled this twenty-first Day of October 1975 [SEAL] Attest:

RUTH c. MASON c. MARSHALL DANN Arresting Officer Commissioner nj'Parentsand Trademarks

2. A photographic element comprising a silver halide emulsion layerwhich is sensitive to a visible region of the spectrum and contains anincorporated color forming coupler, said layer being coated upon asurface on a paper support, said surface comprising polyethyleneimpregnated with an ultraviolet radiation absorbing compound which doesnot emit any substantial amount of absorbed radiation in the visibleregion of the spectrum, said polyethylene surface having an averagereflectance of no more than about 25 percent over wavelengths in theultraviolet region of the spectrum in the range of about 360 to about400 millimicrons and at least about 60 percent, at a wavelength in thevisible region of the spectrum in the range of about 420 to about 500 mMu .
 3. A photographic element of claim 1 in which said silver halideemulsion has coated thereon an ultraviolet radiation absorbing compound.4. A photographic element of claim 1 in which said silver halideemulsion layer contains a hydroxy-substituted aromatic antistain agent.5. A photographic element comprising a silver halide emulsion layerwhich is sensitive to a visible region of the spectrum and conTains anincorporated color forming coupler, said layer being coated upon asurface on a paper support, said surface comprising polyethyleneimpregnated with titanium dioxide, said polyethylene surface having anaverage reflectance of no more than about 25 percent over wavelengths inthe ultraviolet region of the spectrum in the range of about 360 toabout 400 millimicrons and at least about 60 percent, at a wavelength inthe visible region of the spectrum in the range of about 420 to about500 m Mu .
 6. A photographic element of claim 5 in which said titaniumdioxide is predominately rutile titanium dioxide.
 7. A photographicelement of claim 5 in which said titanium dioxide is employed in aconcentration of from 50 milligrams to about 3 grams per square foot. 8.A photographic element of claim 1 in which the ultraviolet radiationabsorbing compound is a benzotriazole.
 9. A photographic element ofclaim 1 in which the ultraviolet radiation absorbing compound is athiazolidone.
 10. A photographic element of claim 1 in which saidcoupler is an incorporated pyrazolone magenta coupler and said visibleregion of the spectrum is the green region.
 11. A photographic elementcomprising: a. a silver halide emulsion layer having a blue sensitivelayer containing an incorporated yellow forming coupler, b. a silverhalide emulsion layer containing a red sensitive layer containing anincorporated cyan forming coupler, and c. a green sensitive layercontaining a magenta forming coupler, d. said layers being coated upon asurface on a paper support, e. said surface comprising a polyolefinimpregnated with titanium dioxide, f. said polyolefin surface having anaverage reflectance of no more than about 25 percent over wavelengths inthe ultraviolet region of the spectrum in the range of about 360 toabout 400 millimicrons and at least about 60 percent, at a wavelength inthe visible region of the spectrum in the range of about 420 to about500 m Mu .
 12. A photographic element of claim 11 in which said titaniumdioxide is predominately rutile titanium dioxide.
 13. A photographicelement of claim 11 in which said polyolefin is polyethylene.
 14. Aphotographic element comprising a developed and fixed photographicemulsion layer containing a developed dye image subject to fading by theaction of ultraviolet radiation, said layer being coated upon a surfaceon a paper support, said surface comprising a polyolefin impregnatedwith an ultraviolet radiation absorbing compound, which does not emitany substantial amount of absorbed radiation in the visible region ofthe spectrum, said polyolefin surface having an average reflectance ofno more than about 25 percent over wavelengths in the ultraviolet regionof the spectrum in the range of about 360 to about 400 millimicrons andat least about 60 percent, at a wavelength in the visible region of thespectrum in the range of about 420 to about 500 m Mu .
 15. Aphotographic element comprising a developed and fixed photographicemulsion layer containing a developed dye image subject to fading by theaction of ultraviolet radiation, said layer being coated upon a surfaceon a paper support, said surface comprising a polyolefin impregnatedwith titanium dioxide, said polyolefin surface having an averagereflectance of no more than about 25 percent over wavelengths in theultraviolet region of the spectrum in the range of about 360 to about400 millimicrons and at least about 60 percent, at a wavelength in thevisible region of the spectrum in the range of about 420 to about 500 Mu.
 16. A photographic element comprising a developed and fixedphotographic emulsion layer containing a developed dye image subject tofading by the action of ultraviolet radiation, said layer being coatedupon a surface on a paper support, said surface comprisinG polyethyleneimpregnated with titanium dioxide, said polyethylene surface having anaverage reflectance of no more than about 25 percent over wavelengths inthe ultraviolet region of the spectrum in the range of about 360 toabout 400 millimicrons and at least about 60 percent, at a wavelength inthe visible region of the spectrum in the range of about 420 to about500 Mu .
 17. A photographic element of claim 16 in which said titaniumdioxide is predominately rutile titantium dioxide.
 18. A photographicelement comprising a developed and fixed photographic emulsion layercontaining a developed dye image subject to fading by the action ofultraviolet radiation, said layer being coated upon a surface on a papersupport, said surface comprising polyethylene impregnated with 50milligrams to about 3 grams per square foot of titanium dioxidepredominately rutile form, said polyethylene surface having an averagereflectance of no more than about 25 percent over wavelengths in theultraviolet region of the spectrum in the range of about 360 to about400 millimicrons and at least about 60 percent, at a wavelength in thevisible region of the spectrum in the range of about 420 to about 500 Mu.